Electronic Structure of Nitric Oxide Adducts of Bis(diaryl-1,2-dithiolene)iron Compounds: Four-Membered Electron-Transfer Series [Fe(NO)(L)2]z (z = 1+, 0
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- 作者：Prasanta Ghosh ; Keira Stobie ; Eckhard Bill ; Eberhard Bothe ; Thomas Weyhermü ; ller ; Michael D. Ward ; Jon A. McCleverty ; Karl Wieghardt
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：January 22, 2007
- 年：2007
- 卷：46
- 期：2
- 页码：522 - 532
- 全文大小：261K
- 年卷期：v.46,no.2(January 22, 2007)
- ISSN：1520-510X
文摘
Four members of the electron-transfer series [Fe(NO)(S2C2R2)2]z (z = 1+, 0, 1-, 2-) have been isolated as solidmaterials (R = p-tolyl): [1a](BF4), [1a]0, [Co(Cp)2][1a], and [Co(Cp)2]2[1a]. In addition, complexes [2a]0 (R = 4,4-diphenyl), [3a]0 (R = p-methoxyphenyl), [Et4N][4a] (R = phenyl), and [PPh4][5a] (R = -CN) have been synthesizedand the members of each of their electron-transfer series electrochemically generated in CH2Cl2 solution. All specieshave been characterized electro- and magnetochemically. Their electronic, Mössbauer, and electron paramagneticresonance spectra as well as their infrared spectra have been recorded in order to elucidate the electronic structureof each member of the electron-transfer series. It is shown that the monocationic, neutral, and monoanionic speciespossess an {FeNO}6 (S = 0) moiety where the redox chemistry is sulfur ligand-based, (L)2-(L
bull.gif">)1-: [Fe(NO)(Lbull.gif">)2]+(S = 0), [Fe(NO)(Lbull.gif">)(L)]0 
f"> [Fe(NO)(L)(Lbull.gif">)]0 (S = 1/2), [Fe(NO)(L)2]- (S = 0). Further one-electron reductiongenerates a dianion with an {FeNO}7 (S = 1/2) unit and two fully reduced, diamagnetic dianions L2-: [Fe(NO)(L)2]2-(S = 1/2).
bull.gif">)1-: [Fe(NO)(Lbull.gif">)2]+(S = 0), [Fe(NO)(Lbull.gif">)(L)]0 f"> [Fe(NO)(L)(Lbull.gif">)]0 (S = 1/2), [Fe(NO)(L)2]- (S = 0). Further one-electron reductiongenerates a dianion with an {FeNO}7 (S = 1/2) unit and two fully reduced, diamagnetic dianions L2-: [Fe(NO)(L)2]2-(S = 1/2).